Mineral oil composition and process of treating same



Patented Mar. 12, 1940 MINERAL OIL COMPOSITION AND PROCESS OF TREATINGSAME Thomas W. Bartram, Nitro, W. Va., assignor to Monsanto ChemicalCompany, St. Louis, Mo.,

a corporation of Delaware No Drawing. Original application September 12,

1935, Serial No. 40,307. Divided and this application September 14,1937, Serial No. 163,825

16 Claims.

This invention relates to improvement in means for the protection ofliquid hydrocarbon products against the formation of insoluble and gummyproducts. More particularly the present invention relates to improvedmaterials foruse Emil; liquid hydrocarbons which may be used as Liquidhydrocarbons as commercially produced, particularly when prepared by thedistillation or cracking of petroleum, possess a tendency on standing toform gums and resinous substances. Gasolines produced by the moderncracking processes are extremely complicated mixtures comprising manyconstituents, the character of these constituents and the relativeproportions of the different constituents depending upon the source ofthe crude and the particular crackin process employed. Among otherconstituents, the crude cracked gasoline contains unsaturatedhydrocarbons, such as for example olefines and diolefines. The morerecent pressure methods of vapor phase cracking resu1t in a considerablyhigher percentage of diolefines than the older methods. It has thusbecome necessary to treat the crude product resulting from the morerecent cracking processes in some manner to remove the greater part ofthese more highly unsaturated products. Among these methods of treatmentmay be mentioned the sulfuric acid treatment and the fullers earth vaporphase treatment. While these methods of purification have beenheretofore largely employed, their use is open to many disadvantages,one of which is the expense involved.

This formation of gummy material in gasoline .causes such undesirableeffects, .when used in internal combustion engines, as sticking of thevalve stems and excessive carbon formation.

In accordance with this invention the development of these undesirablecharacteristics may be readily prevented or materially delayed withoutapparently increasing the cost of production thereof.

The present invention has for an object the inhibition of the formationof gums and resins in 6 oil compositions.

means and special compositions disclosed herein are likewise adaptablefor use as a transformer oil, as a lubricating means, as a heatcirculating medium and analogous uses wherein it is desirable that animproved and satisfactory stable,

mineral oil product be employed.

Another object is to provide a method and means of the characterreferred to that will not appreciably increase the cost of production ofpetroleum products.

Other objects of the invention will be apparent from the followingdescription.

The class of materials which have been found to possess the desirablequalities set forth in that small proportions thereof when incorporatedin a relatively unstable oil product, for example gasoline, materiallyincreases the stability thereof, comprise sulfurized diaryl arylenediamines, or more particularly the reaction products obtainable byreacting a diaryl arylene diamine with sulfur or compounds containingreadily reactive sulfur.

Illustrative of the class of diaryl arylene diamines from whichsulfurized compounds may be prepared and employed as stabilizers forunstable mineral oil products, for example gasoline,

are diphenyl-p-phenylene diamine, diphenyl-mphenylene diamine,diphenyl-o-phenylene diamine, di para tolyl-p-phenylene diamine, di betanaphthyl-p-phenylene diamine, di alpha naphthyl-p-phenylene diamine,aryl substituted naphthylene diamines such as 1.4 dianilino'naphthalene, sym. diphenyl benzidine and analogues and equivalentsthereof. The diaryl arylene diamines of the present invention preferablypossess the formula of In orderto test the gum inhibiting'properties ofthe preferred class of materials, the following procedure which isessentially that described by Egloff, Morrell, Lowry, and Dryer, inIndustrial and Engineering Chemistry, vol. 24, pages 1375 to 1382(1932), was employed.

.In a suitably sized bomb of the type described in the above article,there was placed an 8 ounce oil sample bottle containing 200 c. c. of anunstable gasoline, as for example vapor phase cracked gasoline to whichwas added 20 mgs. of one of the inhibitors of the invention. The lid wasthen placed tightly on the bomb. Substantially one hundred poundspressure of oxygen was introduced into the bomb by means of a suitablevalve. The bomb was then connected, by means of 'a delivery tube, with arecording pressure gauge, after which it was heated in a steam bathuntil a sharp drop in the pressure curve indicated an end of the periodof stability of the unstable fuel, and a rapid reaction of the oxygenwith certain unsaturated compounds in the gasoline. This period ofstability is frequently called the induction period.

As one specific embodiment of the present invention, 26 parts by weightof diphenyl-pphenylene diamine (substantially 0.1 mol) and 12 parts byWeight of sulfur (substantially 0.4 atomic weight portion) were heatedin the presence of a suitable catalyst or condensing agent, for exampleiodine, at the fusion temperature of the mixture. After extracting thereaction product with a convenient solvent, as for example acetone, andseparating the solvent from the extract, the product so produced wasfound on testing in the manner described above to possess an inductionperiod of 450 minutes as compared to the induction period of 60 minutesfor the untreated gasoline.

Di alpha naphthyl-p-phenylene diamine has also been reacted with sulfur,preferably in the ratio of substantially one molecular proportion of dialpha naphthyl-p-phenylene diamine and substantially four atomic weightportions of sulfur, by heating said reactants at a temperature ofsubstantially 200 to 220 C. in the presence of a condensation agent asfor example iodine. The product obtained by this sulfurization processwas found on testing in a vapor phase cracked gasoline to possess thedesirable gum inhibitingproperties typical of the preferred class ofmaterials.

Other methods of preparing the new class of compounds may be employed.Thus, the diaryl arylene diamine may be dissolved or suspended in asuitable high boiling solvent, for example xylene, and reacted withsulfur in the presence of a suitable catalyst, for example iodine. Thus,substantially one molecular proportion of diphenylp-phenylene diamineand an excess over four molecular proportions of sulfur were heated inthe presence of a solvent, as for example xylene, at refluxingtemperature in the presence of a catalyst, as for example iodine, andthe reaction product obtained on testing 20 mgs. thereof in 200 c. c. ofa vapor phase cracked gasoline in the manner described above was foundto possess an induction period of 405 minutes as compared to aninduction period of 60 minutes for the same untreated gasoline.

As a further test showing the gum inhibiting properties of the preferredclass of compounds, a copper dish test was carried out in the well-knownmanner on a vapor phase cracked gasoline containing the preferredgum-inhibitors and on the same untreated gasoline. Thus, as one suchtest, 10 mg. of the reaction product obtained by heating substantiallyone molecular proportion of diphenyl-p-phenylene diamine withsubstantially on a steam bath. The gum formed was 0.0165

gram. A similar test carried out on the untreated gasoline produced0.5327 gram of gum.

Sulfurized diaryl arylene diamines have been prepared by reactingdifferent proportions of amine and sulfur or the sulfur containingcompound than that described above. Thus, a diaryl arylene diamine, forexample diphenyl-p-phenylene diamine, has been reacted with sulfur intheratio of substantially two molecular proportions of a sulfurizingagent, for example sulfur. Furthermore, sulfur chloride, for examplesulfur dichloride, has been reacted with diaryl arylene diamines invarying proportions, and the product so formed employed as inhibitors ofgum formation according to the present invention.

As further specific examples showing the use of the preferred class ofmaterials, the following compounds have been prepared and employed in anunstable vapor phase cracked gasoline in the manner indicated above. (A)reaction product of substantially one molecular proportion of di betanaphthyl-p-phenylene diamine and substantially four atomic weightportions of sulfur; (B) reaction product of substantially one molecularproportion of di-p-tolyl-p-phenylene diamine and substantially fouratomic weight portions of sulfur; (C) reaction product of substantiallytwo molecular proportions of di beta naphthyl-pphenylene diamine andsubstantially one molecular proportion of sulfur dichloride; (D)reaction product of substantially equi-molecular proportions ofdiphenyl-p-phenylene diamine and sulfur dichloride; (E) reaction productof substantially two molecular proportions of di-p-tolylp-phenylenediamine and substantially one molecular proportion of sulfur dichloride;(F) reaction product obtained by heating substantially one molecularproportion of diphenyl-p-phenylene diamine and substantially two atomicweight portions of sulfur at a temperature of substantially 180 to 200C.

Gum inhibitors designated as (A) and (B) above were prepared by heatingthe reactants in the presence of a solvent in a manner analogous to thatdescribed above for the reaction between sulfur and diphenyl-p-phenylenediamine. Gum inhibitors designated as (C), (D) and (E) above wereprepared preferably by carrying out the reaction in the presence of aninert solvent at a temperature below room temperature, preferably at 0to 5 C. in a manner analogous to that described by A. Michaelis and K.Luxembourg in Berichte der Deutschen Chemischen Gesellschaft, vol. 28,pages 165-167 (1895).

The test results follow:

Induction period in minutes 0. c. of vapor phase cracked gasoline Weightof gum inhibitor added, milligrams,

Gum inhibitor assess From the data hereinbefore set forth it is shownthat sulfurized diaryl arylene diamines comprise an important class ofstabilizers of mineral oil products, for example unstable crackedgasoline.

If convenient or desirable, if the inhibitor to be added to the unstableoil product, for example gasoline, is not readily soluble therein, itmay be dissolved in a suitable solvent and the solution of the inhibitorthus prepared added thereto.

Other similar oil compositions designed for particular uses may beprepared in the manner described by substituting the desired oilfraction or cutand'adding the necessary quantity of the gum inhibitorthereto. To produce the effect desired, a quantity of inhibitor equal tofrom 0.001 to 0.05% of the weight of the oil product is preferablyemployed.

, Other ratios of the preferred class of materials than thosehereinbefore set forth have been incorporated in an unstable oilproduct, for example gasoline. v

The present invention is limited solely by the claims attached'hereto aspart of the present invention.

This is a division of my co-pending application Serial No. 40,307 filedSeptember 12, 1935.

What is claimed is:

1. A cracked hydrocarbon motor fuel of the type which tends todeteriorate on storage as evidenced by color and gum formationcontaining as a stabilizer thereof a small proportion of a sulfurizeddiaryl arylene diamine obtainable by reacting a sulfur halide consistingof the elements sulfur and halogen and a diaryl arylene diamine in thepresence of a substantially inert solvent and at a low temperature.

. 2. A cracked hydrocarbon motor fuel of th type which tends todeteriorate on storage as evidenced by color and gum formationcontaining as a stabilizer thereof 'a small proportion of a sulfurizeddiaryl phenylene diamine obtainable by reacting a sulfur halideconsisting of the elements sulfur and halogen and a diaryl phenylenediamine in the presence of a substantially inert solvent and at a lowtemperature.

3. A cracked hydrocarbon motor fuel of the type which tends todeteriorate on storage as evidenced by color and gum formationcontaining as a stabilizer thereof a small proportion of a sulfurizeddiaryl arylene diamine obtainable by reacting substantially twomolecular proportions of a diaryl arylene diamine and at least onemolecular proportion of a sulfurhalid consisting of the elements sulfurand halogen in the presence of a substantially inert solvent and at alow temperature.

4. A cracked hydrocarbon motor fuel of the I type which tends todeteriorate on storage as evidenced by color and gum formationcontaining as a stabilizer thereof a small proportion of a sulfurizeddiaryl phenylene diamine obtainable by reacting substantially twomolecular proportions of a diaryl phenylene diamine and at least onemolecularproportion of sulfur dichloride in the presence of asubstantially inert splve'iit and at a low temperature.

5. A cracked hydrocarbon motor fuel of the type which tends todeteriorate on storage as evi- 4 idenced by color and gum formationcontaining as a stabilizer thereof a small proportion of a sulfurizeddi-p-tolyl p-phenylene diamine obtainable by reacting substantially twomolecular proportions of di-p-tolyl-p-phenylene diamine andsubstantially one molecular proportion of sulfur dichloride in thepresence of a substantially inert solvent and at a temperature ofsubstantially 5 C. to C.

7. A cracked hydrocarbon motor fuel of the type which tends todeteriorate on storage as evidenced by color and gum formationcontaining as a stabilizer thereof a small proportion of a sulfurized dibeta naphthyl-p-phenylene diamine obtainable by reacting substantiallytwo molec ular proportions of di beta naphthyl-p-phenylene diamine andsubstantially one molecular proportion of sulfur dichloride in thepresence of; a substantially inert solvent and at a temperature ofsubstantially 0 C. to 5 C.

8. A cracked hydrocarbon motor fuel of the type which tends todeteriorate on storage as evidenced by color and gum formationcontaining m as a'stabilizer thereof a small proportion of a sulfurizeddiphenyl-p-phenylene diamine obtainable by reacting substantially onemolecular proportion of diphenyl-p-phenylene diamine and substantiallyone molecular proportion of sulfur dichloride in the presence of asubstantially inert solvent and at a temperature of substantially 0 C.to 5 C. r

9. A cracked gasoline containing as a. stabilizer thereof a smallproportion of a sulfurized diaryl 30 arylene diamine obtainable byreacting a sulfur .halide consisting of the elements sulfur andhaldiaryl arylene diamine obtainable by reacting substantially twomolecular proportions of a diaryl arylene diamine and at least onemolecular proportion of sulfur dichloride in the presence of asubstantially inert solvent and at a low temperature.

12. A cracked'gasoline containing as a stabilizer thereof a smallproportion of a sulfurized diaryl phenylene diamine obtainable byreacting substantially two molecularproportions of a diaryl phenylenediamine and at least one mole- 5 cular proportion of sulfur dichloridein the presence of a substantially inert solvent and at a lowtemperature.

13. A cracked gasoline containing as a stabilizer thereof a smallproportion of a sulfurized o diphenylw-p-phenylene diamine obtainable byreacting substantially two molecular proportions of adiphenyl-p-phenylene diamine and at least one molecular proportion ofsulfur dichloride in the presence of a substantially inert solvent andat a temperature of substantially 0 C. to 5 C.

14. A cracked gasoline containing as a stabilizer thereof a smallproportion of a sulfurized di-p tolyl-p-phenylene diamine obtainable byreacting substantially two molecular proportions ofdi-p-tolyl-p-phenylene diamine and substantially one molecularproportion of sulfur dichloride in the presence of a substantially inertsolvent and at a temperature of substantially 0 C.- to 5 C.

15. A crackcd'gasoline containing as a stabilizer thereof a smallproportion of a sulfurized diphenyl-p-phenylene diamine obtainable byreacting substantially one molecular proportion of diphenyl-p-phenylenediamine and substantially one molecular proportion of sulfur dichloridein the presence of a substantially inert solvent and at a temperature ofsubstantially 0 C. to 5 C.

THOMAS W. BARTRAM.

